Fungicidal composition



Patented Nov. 21, 1950 ["UNGICIIDALv COMPOSITION Sever L. llopperstead,Brighton, Mich assignor to The B. F. Goodrich Company, New York, N. Y.,a corporation of New York No Drawing.

Application September 6, 1948,

Serial No. 095.291

2 Claims. I (01. 107-42) This invention relates to fungicidalcompositions and to the treatment of plants therewith, and moreparticularly to new compositions which can be applied to the non-edibleportions of foodproducing plants to protect them from the destructionand deterioration caused by fungi and bacterial diseases. 7

The fungicidal compositions of this invention comprise an aqueousdispersion of a polyalkylene polysuliide admixed with a quaternaryammonium salt derived from a heterocyclic tertiary amine preferably onecontaining a six-membered ring consisting of one tertiary nitrogen atomand five carbon atoms wherein the nitrogen atom is connected to onecarbon atomby a single bond and to another carbon atom by means of adouble bond. I have found that the alkyl quaternary ammonium salts ofthese heterocyclic tertiary amines when used in combination with anaqueous dispersion or an alkylene polysulfide preferably polyalkylenepolysulflde. are particularly effective in combating the destruction anddeterioration to the non-edible portion of food-producing plants broughtabout by fungi and bacterial diseases.

My new compositions are prepared by mixing an aqueous solution of aquaternary ammonium salt of any of the above-defined six-memberedheterocyclic tertiary amines with an aqueous dispersion of apolyaikylene polysulflde preferably an aqueous latex-like dispersion ofpolyethylene polysulfide. The preferred polysuliide dispersions can beprepared by condensing ethylene dichloride with sodium polysuliide inthe presence of a salt-stable emulsifying or dispersing agent such ascasein, sodium and calcium lignin sulfonates, alkyl benzene sulfonateshaving more. than carbon atoms in the alkyl group, aryl alkylsulfonates, sorbitan monolaurates and others. The preferred emulifyingagent is sodium lignin sulfonate, for extremely stable latexlikedispersions can be prepared by employing this emulsifying agent. Theresulting polyethylene polysulfide is allowed to settle or caused tosettle by flocculation, is washed with water by decantation to removethe sodium chloride formed during the condensation, and is redispersedor reemulsiiied by adding water and stirring. g

The quaternary ammonium salts which may be employed according to myinvention include, for example, the methyl. ethyl, butyl, propyl, amyl,octyl, decyl, lauryl and cetyl chlorides, bromides, iodides, rhodonatesand acetates of such sixmembered heterocyclic amines as pyridines.quinolines, isoquinolines, acridines, and the like. Other quaternaryammonium salts of such amines 2 wherein the acid radical is any otherinorganic or organic monovalent acid radical may also be used.

The concentration of the quaternary ammonium salt in the mixture may bevaried as desired to meet special conditions, but usually a lesseramount of the quaternary salt than of the polysulfide is employed. Ingeneral, about 1 part by weight of quaternary salt to about 5 to 50parts by weight of polysulflde, which is present in about 500 to 5,000parts of aqueous dispersion, is sufficient for most uses. It should beunderstood, however, that compositions containing a lesser or greateramount of water, and in which the ratio of quaternary salt topolysulfide may be varied from as little as l to 1,000 or even less toas much as 1 to 1 or even more, are also within the scope of thisinvention since the proportions of the ingredients of my newcompositions are in no way critical.

To illustrate the invention, the following speciflc composition wasemployed successfully to control apple scab and tomato blight.

Four pounds of an aqueous dispersion containing 50% polyethylenepolysulfide by weight was diluted to gallons with stirring. To thisdilute aqueous dispersion there was added one pound of an aqueoussolution containing 20% by weight of lauryl isoquinolinium bromide. Theresulting mixture was stirred for about 30 minutes to insure completemixing of the components.

This mixture containing lauryl isoquinolinium bromide and an aqueousdispersion of polyethylene polysulflde was sprayed on a group of appletrees in an orchard infested with the devastating apple scab which isinduced by the parasitic fungus Venturia inaequalis (Eke.) Aderh. Thecontrol of the apple scab was complete for all trees sprayed with thiscomposition.

The above composition was sprayed on tomato plants which were infestedwith tomato blight. The control of the tomato blight was complete forall the sprayed plants.

An aqueous solution containing lauryl isoquinolinium bromide alone inthe same concentration as used above was also sprayed on apple treesinfested with apple scab and tomato plants infested with tomato blight.It was found that lauryl isoquinoline bromide alone gave only a 33%control. An aqueous dispersion of polyethylene polysulfide alone in thesame concentration as above was also tested in the same manner and gavea control of about 50%. Thus, it is apparent that the effectiveness ofeach of the constituents was enhanced by combining them.

The reasons for the synergistic effect observed bymsing a compositioncomprising both the polyalkylene polysulflde and the quaternary salt arenot known with certainty. It is thought that the quaternar salt maychemically combine with the polyalkylene polysulflde to produce a newchemical of remarkable fungicidal activity. Regardless of whether such achemical combination occurs, however, it has been found that merelyadmixing the polyalkylene polysulilde dispersion with the quaternarysalt produces a composition which is far superior as a fungicide toeither of the materials alone.

My compositions are also capable of protecting food-producing plantsfrom other fungi and bacterial diseases. For example, my compositionscan be employed to combat such plant diseases as cherry leaf spot,Coccomuces hiemalis Hig., brown rot, Sclerotina jructicola (Wint.),Rehm, and Sclerotina americana (Wormald), Norton and Ezekiel, andothers. They are also effective against fungus diseases of flowers andare useful in preventing mildew of fabrics and in various otherfungicidal applications.

While I have disclosed specific examples of my invention, I do notthereby desire nor intend to limit myself solely thereto, for, ashitherto stated, other equivalent chemical compounds can be employed andthe proportions of the active ingredients may be varied if desiredwithout departing from the spirit and scope of my invention as definedin the appended claims.

I claim:

1. A fungicidal composition containing as the essential activeingredients polyethylene polysulflde and lauryl isoquinolinium bromidedispersed in an aqueous solution of sodium lignin 4 sulfonate, therebeing present in said composition about one part by weight of thebromide for each 1 to parts by weight of the polysulflde in 500 to 5,000parts by weight of aqueous dispersion.

2. A fungicidal composition containing as the essential activeingredients polyethylene polysuliide and lauryl isoquinolinium bromidedispersed in an aqueous solution of sodium lignin sulionate, there beingpresent in each gallons of said composition about 1 part by weight ofsaid bromide compound and about 10 parts by weight of the polyethylenepolysulfide.

SEVER. L. HOPPERSTEAD.

REFERENCES CITED The following references are of record in theme of thispatent: I

UNITED STATES PATENTS OTHER REFERENCES Wadley: U. S. D. A. ET-223 June1945, The Evidence Required to Show Synergistic Action of Insecticides,"7 pages.

Mfg. Chemist and Mfg. Perfumer, October 1945, XVI, 10, pages 356-357.

1. A FUNGICIDAL COMPOSITION CONTAINING AS THE ESSENTIAL ACTIVE INGREDIENTS POLYETHYLENE POLYSULFIDE AND LAURYL ISOQUINOLINIUM BROMIDE DISPERSED IN AN AQUEOUS SOLUTION OF SODIUM LIGNIN SULFONATE, THERE BEING PRESENT IN SAID COMPOSITION ABOUT ONE PART BY WEIGHT OF THE BROMIDE FOR EACH 1 TO 50 PARTS BY WEIGHT OF THE POLYSULFIDE IN 500 TO 5,000 PARTS BY WEIGHT OF AQUEOUS DISPERSION. 